Process of sizing textiles, the size, the preparation of the same, and the sized article



' 20 kink ,or waviness Patented- Oct. 22 1940 PATENT OFFICE mam-- "rnocnss or SIZING 'rax'rlms, ran

SIZE,

-THE PREPARATION OF THE SAME, AND

-mcya:w. can, Bloomfield, n. 1., and mat Segessemann, cedar-town tional Oil Products Harriso a corporation of New Jersey Application January 12, 1938, Serial No. 184,542

v No Drawing.

, GM auignors to Na- 1a cam (oi. 134-18) The invention relates, in general, to a process of sizing textile materials and. in particular, to

a process of sizing synthetic, yarns in the pro- 5 related improvements in sizing materials employed in. such process.

Synthetic fibers in crepe-type fabrics, are characterizedby being somewhat plastic in nature and elongate or stretch readily .when Subjected to tensile forces of a degreefe'qual to that normally employed in f the processing thereof I or [in the. fabrication of goods therefrom. Synthetic yarns, filaments,

threads. etc.,;are not inherentlyfcapable of retaining or storing the energy imparted thereto during'the twisting step in the manufacture of crepe fabrics with the result that the desired Moreover, these Jtextlle materials show a loss in denier whensublected to the aforementioned elongation or twisting, and also exhibit as a result of such deformation a decreased pliancy,

25 and decreased amnity for dyes.

In an attempt to overcome th foregoing difil culties,.it is now customary to size or otherwise" apply aprotective coating around filamentary bodies composed of synthetic materials before lo processing and/or fabricating goods therefrom.

In the manufacture ofwoven-crepe fabrics, for

' example, the desired number of warp threads arefjs'ized and wound upon abeam in the 'usual manner. The weft orfilling threads, are the elements in the completed crepe fabric that impart the crepe effect thereto and their preparation usually comprises subjecting a synthetic thread, yarn, filament or-the like, to the following steps;

I. soaking, 2. conditioning, 3. spinning and twist- Q ing, 4.'twist setting, and '5. copping or quilling. I

Syntheticfibers are manufactured in 'various sized filaments, anumber of whlch'are combined with. a slight twist to produce. a yarnhaving may vary from 100F300 deniers.

filling yarns thefirst step comprises soaking skeins of the yarn in afiuid composition com- ;5o,prising, a;water-soluble materiaL/such' as glue,

gelatinegetccand a softener or, plasticizer therefon after which the yarn is hydro-extracted and dried. The. second operation comprises conditioning the yarn in a humidified atmosphere so- 55 that the yamwili regain its normal moisture duction of crepe fabrics therefromand to cor I the form of filaments," threads,yarns, etc., of the typefiemployed in the manufacture of woven fabrics, particularly the;

effect inthe finished fabric.

called crepe is not obtained.

content and thus prepare it for the third step of spinning, during which a twist is imparted to the yarn that may runes high as 65 or more turns per inch. It might be stated here that I usually about one-half of the filling yarns are 5 given a right-handttwist and the remaindera left-hand twist so as to impart the desired. crepe The fourth. step involves setting of the twist by subjecting the twisted yarns to an atmosphere of, steam and 10 pressure for a'suitabie period of time after which the fifth step of copping is carried out, i. 'e.-, rewinding the yarn from spools onto quills, cops, shuttle bobbins or the like. -A warp and the filling threads prepare in the 15 above-described manner are woven into fabric having any desired design, count, width, etc., the left and right-hand twisted filling threads being alternated singly or in groups ofany desired number. Aftemthe fabric has been woven, it is subjected to a so-called boil-off or scouring operation wherein the sizing material is dissolved or emulsified and removed from the fibers, thus 1 allowing the filling threads to spring back to their most natural condition and thereby producing a kinked or creped effect in the resulting fabric.

While the herein before described procedure is being practiced with varying degreesof success, the fact remains that many difficulties arise so therefrom. For example; (a) the sizing compositionin the bathtends to decompose due to bacterial action, (b) the viscosity of the sizing bath is changed due to heating, and reheating thus affecting the thickness of the film applied to the yarns, (c) the strength of the film-form-, ing'constituent is affected by ageing and heating the bath, (11) these changes in the proper-. ties of the bath render successive skeins of yarn non-uniform, (e) the'si'zing is' not readily re- 40 1 moved from'the fibers at the proper time, (1)

theresulting crepe or pebbleeffect is not even or deep enough, etc.; and in view of these and other disadvantages, there is a constant. demand for improved sizes and improved processes of producing crepe-effects in woven and other fabrics.

The general object of theinvention isto ob viate the foregoing and other difficulties .in the art.

Another object of the invention is to; pro,- vide an improved process of sizing yarns, filaments, threads and the like in preparation for their fabrication into textiles. v v

. A specific object of theinvention is-to' proess of applying the same so as to' produce a crepe fabric having improved crepe or pebble eilects. 4

Another specific object of the invention is to provide a size which is substantially resistant,

to bacterial decomposition and which may be readily removed from the yarns during the boilofi 'or desizing operation.

A further objectof the invention is to provide a sizing composition which may be heated and reheated for relatively long periods of time without deleteriously afiecting theviscosity of the sizing bath or the film strength of the filmforming constituent or constituents contained therein. I

Other objects will in part be obvious and will in part appear hereinafter.

According to the invention, there is provided a sizing composition comprising a sulfonated condensation product of an aromatic hydrocarbon, derivative or homologue thereof with a terpene hydrocarbon, alcohol, ketone, ester or other suitable'terpene derivative and a plasticizer therefor such as a suitable sulfonated body or mixture of bodies. The invention further comprises applying the novelsizing composition of the in-- vention to synthetic yarnsin the manufacture of textile materials, more particularly crepe fabrics.

The invention accordingly comprises the several steps and relation of one or more of such' steps with respect to each of 'the others, anda composition of matter possessingthe characteristics, properties and relation of components, all

of which will be exemplified in the following detailed disclosure, and the scope of the invention will be indicated in the claims.

. preferably composed of a-hydrophilic colloidal material such as regenerated cellulose which may be obtained in a known anner from viscose, cuprammonium solutions of cellulose, or by the partial or complete de-esterification of cellulose esters or by other suitable processes. ()ther water or alkali swelling cellulose .derivatives may also be used as filling threads such as alkali soluble cellulose ethers and the like.

The film-forming constituent in the sizing composition may comprise any suitable water soluble product obtained by the sulfonation of a condensation product of a terpene or derivative thereof with any suitable aromatic hydrocarbon or their homologues. More, specifically. the filmforming ingredient may comprise a sulfonated product derived from the condensation of any suitable mono or polynuclear hydrocarbon or homologue such, for example, as benzene, toluene, xylene, naphthalene, phenols, cresols, amines, naphthols, etc., as well as their corresponding sulphonated derivatives, with any suitable open chain or cyclic terpenes or their alcohols, ketones, esters, etc. such, for example, as terpin, terpin hydrate, pinene, terpinene, terpin- ,olene, dipentene, terpineol, borneol, fenchyl alcohol, etc., or with crude materials rich inter- 2,218,500 vide an improved size and a commercial proc-- pen'es or terpene alcohols such as turpentine and pine oil respectively. The expression terpenic compound is used generically in the present specification and claims to describe the terpenic bodies of the aforementioned type. Sulfonation of.the' condensation product may be dispensed with in some instances where the hydrocarbon employed in the condensation is pre-sulfonated. The-aforementioned condensation products may be modified by further condensation with a compound which is capable of reacting with two molecules of the substituted sulphonic acid by forming a carbon or sulfur bridge between two aromatic nuclei, such for example as aliphatic aldehydes as formaldehyde or acetaldehyde, etc., aromatic aldehydes as benzaldehyde, etc., ketones as acetone, etc. or sulfurhalides as sulfur-monochloride, etc. 1

The condensation product may be sulfonated either during the condensation process or subse quently thereto by any suitable sulfonating agent, such as sulfuric acid, fuming sulfuric acid, acetyl sulfuric acid, chlorsulionic acid, oleum, etc., or the hydrocarbon may be sulphonated prior to the condensation process.

' For a fuller understanding of the nature of the water-soluble film-forming constituent employed in the sizing composition of the invention, the following examples are given to illustrate suitable methods of producing the same and they are not to be construed in a limiting sense.

Example I ter containing 200 grams of sodium chloride. In

about two hours separation takes place and the sulfonation mass (bottom layer) is drawn oi! and neutralized with NaOH and solvent removed.

Example II To a mixture of 108 parts of .M-cresol and 154 parts of turpentine are added slowly ,and with rapid stirring at C. to C. 210 parts of 100% sulphuric acid. The mixture is well stirred for two hours and is then allowed to stand at room temperature for 24 hours. The reaction mass which is now clearly soluble in water is then washed substantially free from acid with salt solution and is then neutralized with caustic soda I solution and the solvent distilledofl.

Example III To a 'solution of 128 parts of naphthalene in 154 parts of pine oil and 300-parts of ethylene chloride are added with rapid stirring between 20 C. and 30 C. 260 partsfoi chlorsulphonic acid.

.The reaction mass is stirred until the evolution of hydrogenchloride has ceased and is then allowed to stand over night at room temperature. The reaction mass is then washed with salt solution, neutralized with soda and the solvent is distilled oil.

' Example IV To a mixture of 108 parts of commercial oresylic acid, 136 parts oi dipentene and 250 parts of pleted when the mass is clearly Somme in which requires about hours. reaction is then vwashed and neutralized and the solvent is distilledofl.

Example V To a mixture of 94 parts of phenolf 154 parts of v pine oil and 200 parts of ethylene chloride are added w-itnrapid stirring 250 parts of fuming sulphuric ac'idQkeepingthe temperature during thereaction between C. and 30 ble 'in water which required about 4' hours. At the end of this period 53 parts of benzaldehyde is added, keeping the temperature-below 30C. The mass is agitated for 2 hours and then allowed to stand for 24 hours without agitation. During and thesolvent is distilled off in 7 20 C. for 4 hours or until 20 C.-30 C. The mass ditional period of 3 hours and is then washed and r 154 parts. of

' fuming sulphuric this time condensation of the benzaldehyde with the substituted sulphonic acids becomes .com-

plete. The mass is then washed and neutralized the usual manner.

Example VI v A mixture of 108 parts of U. S. P. cresol, 154 parts ofturpentine, 250 parts of ethylene chloride and 260 parts of chlor-sulphonic acid are sub jected to reaction at a temperature of 15, C.-

the product is clearly soluble in water. 68 parts or sulphur monochloride is then added slowly and with rapid stirring,

is maintained between isthen stirred for an adwhile the temperature finished as cited in Example I.

' Example VII To a solution of 128v parts of naphthalene in pine oil and 200' parts of ethylene chloride'are added-with rapid stirring at 20 C.-

30" C. 300'parts of chlorsulphonic acid. The mixture is'then allowed to stand at room tempera-'- ture for 24 hours. Atthe end of this period the reaction mass is diluted with 100 parts of water and 38 parts of a 40% formaldehyde solution are then added slowly and with stirring. During this operation the temperature is keptbetween 20 C. and 40 C. The mass is then stirred for- 1 hour or until the formaldehyde odor has completely disappeared. The product of reaction is thenwashed in salt solution and'neutralized and the' solvent is distilled off. I

Example vm sulphonic acid by acting on it with 100 parts of acid at 100 C. vThereupon the reaction mixture is cooled to 20 C. and a solution of 154 parts of alpha-terpineol in 200 parts of ethylene chloride is added. The mixture is then agitated and while maintaining the temperature between 15 C. and 20 C'., 100 parts of fuming sulphuric acid are added. The mixture,

Example IX I 108 parts of M-cresol are converted into the corresponding sulphonic acid by acting on it with 200 parts of sulphuric acid'at C.

a las s,

The product of.

. C. The reaction is .completedwhen the mass is clearly solu-.

arts of toluene are converted into toluene 1 Water reaction mixture is then cooled to 20' C. and a-solutionof I54 stirred well and then 100 parts of fuming sulphuric acid are added, keeping the temperature between 15- C. and 20" C. At the-end of six hours-the product of reaction is poured into 000 parts of a 20% salt. solution and well agiated. The mass separates into two layers, the lower of-which containing the sulphonated condensation product-is withdrawn and neutralized with a caustic potash solution and the solvent distilled ofl.

- Example X a i To a mixture of 208 parts of naphthalene sulphonic acid and 200 parts of ethylene chloride are added with rapid stirring at 20 C.'30'C. 154 parts of pine oil, followed by 100. parts of chiorsulplionic acid. The mixture is then al.- lowed to stand for 24 hours. At theend of this period the reaction mass is diluted with 100 parts of water and 38 parts of 40% formaldehyde solution are then added slowly and with stirring, lreeping the. temperature between 20 C. and 40 C. The-mass is then stirred for 1 hour or until the formaldehyde odor has completely disappeared. The product of. reaction is then I parts of pine oil in 200 parts of carbon tetrachlorideis added. The mixture is washed in salt solution and neutralized and the solvent is distilled off.

. Inpreparing the sizing composition. of the in- .vention a desired amount of a condensation product, of the type hereinbefore described, is admixed with or otherwise has incorporated therein, a

suitable plasticizer therefor, such for example as sulfonated .castor oil soap, sulfon'ated cocoanut oil, or any other suitable sulfated fatty oil, wax

or soap thereof, as wellas mahogany soaps, sulfated alcohols, pine oil or any mixture of these or other substances, whichfunction to effectively soften or plasticize the sizing deposited on the yarn so that the original pliability or'fiexibility of theyarn will not be materially affected.

, For a fuller understanding of the nature and the objects of the invention, reference is made to the following specific examples of the sizing composition of the invention and their application with respect to the treatment of textiles. It is to beunderstood that .theseexamples are given merely to illustrate the invention and they should so not be construed in a limiting sense;

Example A product obtained as in Example. I "(dry weight)' 9 Sulfonated castor oil soap do 3 500 A"regenerated-cellulose filling yarn denier position and'dried: The sized yarn i'sthen conditioned, twisted and finally woven with a suit- 4 Pounds Sulfonated cresol-pine oil condensation '40 filament Bright) is soaked in the above com- 6 able warp into a 96x50; 4x4 crepe fabric which is subsequently scoured toremove the size. The resultingcrepe fabric is characterized by having a fine even, deep pebble presenting an enhanced appearance with respect to prior crepe fabrics.

' v Example B Pounds Sulfonated cresol-turpentine condensation product obtained as in Example II.. "(dry weight) a 10 Sulfonated sperm 'oil do 503 Water I A 96x50 fabric having a 2x2 crepe produced from a filling yarn (150 denier 40 filament Bright) sized with the above composition, in accordance with the process under Example A, exhibits an even and, deep pebble effect. A deeper, finer and more regular pebble eifect may be obtained by employing A; the amount of plasticizer (sulfonated sperm oil) given above, when the filling yarn iswoven into a 111-52 2x2 crepe fabric.

. Example Pounds Sulfonated condensation product obtained as in any of-Examples I to X (clry weight) 3 Sulfonated fatty oil or wax do e 2 Water 500 v Creped fabrics produced from filling yarn sized with any of the above compositions even pebble and full hand.

Example D As a warp sizing the following composition may be used:

Pounds Sulfonated condensation product (dry weight)' 35 Sulfonated castor oil and pine oil 500 This particular composition has proven in sizing cellulose acetate warp yarns.

It is within the purview of the invention to I applythe size to the yarns in any suitable manner as by soaking a skein in a bath or\by continuously running the yarn through a bath or over a coated roller or by spraying or in any other suitablemanner. The same bath may be used continuously or intermittently from day to day and the concentration of the solids may be kept within the operable percentage range by periodically adding given quantities of the condensation1product and plasticizer.

Many advantages over the heretofore known practices result from employing the 'hereindescribed invention, a few of ated as follows:

1. More even and deeper pebble effects are obtained in the finished crepe fabrics. For example, a 150 denier yarn gives pebble effects equivalent to that heretofore obtained with a 200 denier yarn.

2. The sizing composition may be subjected to repeated-heatings and may be used for a prolonged period of time without materially affecting its film strength or viscosity.

3. The sizing composition is not subject to bacterial decomposition as is commonly the result when using glue, gelatine and like materials.

which are enumerduring thescouring operation.

.5. The film-forming constituent displays certain wetting properties which aids in obtaining a more even sizing.

6. The film-forming constituent is produced synthetically from relatively pure raw materials thereby assuring uniformity in the sizing from batch to batch.

The expression yarn" is used herein to include yarns, threads, filaments, fibers and like textile materials.

.Bince certain changes in carrying out the above process and certain modifications in the composition which embody the invention may be made without departing from its scope, it is inamasoe present an valuable 4. The sizing is readily removed from the yarns yarns for weaving into a crepe fabric, the step tended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended to cover all the generic and 5 specific features of the invention herein described and all statements of the scope of the invention, which, as a matter of language, might be said to fall therebetween; and that they are intended to be inclusive in scope and not exclusive, in that if desired other materials may be added toour novel composition of matter herein claimed without departing from the spirit of the invention.

:Particula'rly it is to be understood that in said claims, ingredients or components recited in the 1B singular are intended to include compatible mixtures of said ingredients wherever the sense permits. Having described our invention, what we claim as new and desire to secure by Letters Patent is: 1. A process of sizing textiles, which comprises applying thereto a s'izingcomposition containing as the film forming constituent a water-soluble v salt of a sulfonated condensation product of a terpenic compound with an aromatic compound selected from thegroup consisting of the mono and polynuclear hydrocarbons and their hydroxy, carboxylic, alkyl, amino and sulfonic acid derivatives.

2. A process of sizing textiles, which comprises applying thereto a sizing composition comprising a water-soluble salt of a sulfonated condensation product of a terpenic compound with an aromatic compound selected from the group consisting of the mono and polynuclear'hydrocarbons and their hydroxy, carboxylic, alkyl, amino and sulfonic acid derivatives as the film forming constituent and a plasticizer therefon' 3. A process of sizing textile yarns, which comprises applying thereto a sizing composition comprising an aqueous solution of a water-soluble salt of a sulfonated condensation product of a terpenic compound with an aromatic compound selected from the group consisting of the mono and polynuclear hyulrocarbons and their hydroxy, carboxylic, alkyl, amino and sulfonic 'acid derivatives; the condensation product serving as which comprises sizing such yarns with a composition containing as the film forming constituent'a water-soluble salt of a sulfonated condensation product of a terpenic compound with as an aromatic compound selected from the group consisting of the mono and polynuclear hydrocarbons and their hydroxy, 'carboxylic, alkyl, amino and sulfonic acid derivatives.

6. In a process of preparing filling yarns for weaving into a crepe fabric, the step which oomprises applying to a yam composed of a hydrophiiic colloidal material, a composition containing as the illmforming constituent a water-soluble salt of a sulfonated condensation product of '5 a terpenic compound with an aromatic compound selected from the group consisting ofthe mono and polynuclear hydrocarbons and their hydroxy, carboxylic, alkyl amino and sulfonic acid derivatives.

7. A'process of preparing filling yarns for weaving into crepe fabrics, comprising sizing a yarn composed of a hydrophilic cellulosic matei'ial with a composition comprising a watersoluble salt of a sulfonated condensation product of a terpenic compound with an aromatic compound selected from the. group consisting of the mono and polynuclear hydrocarbons and their hydroxy, carboxylic, alkyl, amino and sulfonic acid derivatives as the film forming constituent and a plasticizer therefor -and twisting the yarn.

8. A process of preparing filling yarns for weaving into. crepe fabrics, comprising sizing a yarn composed of a hydrophilic cellulosic material wtih a composition comprising a watersoluble salt of a sulfonated condensation product of a cresol with turpentine as the film forming constituent and a plasticizer therefor and twisting theya'rn.

9. A process of preparing filling yarns for weaving into crepe fabrics, comprising sizing a yarn 'composedof a hydrophilic cellulosic material with a composition comprising a watersolub-le salt of a sulfonated condensation prod not of a cresylic acid with pine oil as the film forming constituent and a plasticizer therefor and twisting the yarn.

10. A process of preparing filling yarns for weaving into crepe fabrics, comprising sizing a yarn'com'posed of a hydrophilic cellulosic material with a composition comprising a watersoluble salt of a sulfonated condensation product of a cresol with pine oil and an aldehyde as the film forming constituent and a plas-ticizer therefor and twisting the yarn. 1

11. A sizing bath for warp and filling ya-rns to be woven into crepe fabrics, comprising an aqueous solution'of a water-soluble salt of a sulfonated condensation product of a terpenic compound with an aromatic compound selected from the group consisting of the mono and polynuclear hydrocarbons and their hydroxy, carbox- 1 ylic, alkyl, amino and sulfonic acid. derivatives as the film forming constituent and a plasticizer for the condensation product.

12. A sizing bath for warp and filling yarns to be woven into crepe fabrics, comprising an derivatives.

aqueous solution of a water-soluble salt of a sulfonated condensation product of cresol with turpentine as the film forming constituent and a plasticizer for [the condensation product.

13. A sizing bath for warp and filling yarns to be woven into crepe fabric-s, comprising anv aqueous solution of a water-soluble salt of a sulfonated condensation product of cresylic acid with pine oil as the film forming constituent and stituent and a plasticizer for the condensation product. I

15. A sizing bath for warp and filling yarns to be woven into crepe fabrics, comprising an aqueous solution of a water-soluble salt of a sulfonated condensation product of a cresol with pine oil and formaldehyde as the film forming constituent and a plasticizer for the condensation product.

16. A textile yarn bearing a size comprising as the film forming constituent a water-soluble salt of a s'ul fonated condensation product of a terpenic compound with an aromatic compound selected from the group consisting of the mono and polynuclear hydrocarbons and their hydroxy, car-boxylic, alkyl, amino and sulfonic acid 17. A filling yarn adapted to be woven into a crepe fabric comprising a twisted yarn bearing a size comprising as the film forming constituent a water-soluble salt of a sulfonated condensation product of a terpenic compound with an aromatic compound selected from the group consisting of the mono and polynuclear hydrocarbonsand their hydroxy, carboxylic, alkyl, amino and sulfonic acid derivatives 18. A filling yarn adapted to be woven into a crepe fabric comprising a twisted hydrophilic cellulosic yarn bearing a size comprising as the film forming constituent a plasticized water-sol- .uble salt of a sulfonated condensation product of a terpenic compound with an aromatic compound 

